Monoazo red dye compound having vinylsulfone type fiber reactive groups

ABSTRACT

A monoazo compound represented by the following formula in the free acid form, ##STR1## wherein D is phenylene or naphthylene, R is hydrogen or alkyl, A is phenylene or naphthylene, Z 1  and Z 2  independently of one another are each vinylsulfonyl, β-sulfatoethylsulfonyl and the like, and X is pyridinio or amino represented by the following formula ##STR2## wherein R 1  and R 2  independently of one another are each hydrogen, alkyl, phenyl, naphthyl or benzyl, which is useful for dyeing or printing fiber materials to give dyed or printed products of red color excellent in fastness properties with excellent build-up, level-dyeing and washing-off properties.

The present invention relates to a monoazo compound, a process forproducing the same and a process for dyeing fiber materials using thesame. More specifically, the present invention relates to a monoazocompound having plural vinylsulfone type fiber reactive groups throughan amino- or pyridinio-substituted triazinyl group, which isparticularly useful for dyeing or printing fiber materials in a redcolor.

Reactive dyes, having a vinylsulfone type fiber reactive group have beenextensively used for dyeing fiber materials, particularly those such ascellulose fibers. However, these known dyes are not yet sufficient tomeet needs of high level for dye performances in a certain dyeing methodsuch as exhaustion dyeing, and for fastness properties of dyed products.

Many kinds of reactive dyes useful for dyeing or printing fibermaterials in a red color are known. For example, U.S. Pat. No. 3,223,470discloses a red reactive dye represented by the following formula in thefree acid form, ##STR3## and Published Unexamined Japanese PatentApplication No. 59-115362 also discloses a reactive red dye representedby the following formula in the free acid form,

However, these known red dyes also are not yet sufficient in theirsolubility, dye performances such as build-up property and the like, andfastness properties such as acid-hydrolysis fastness, chlorine fastnessand the like, and are awaiting for improvements.

It is natural that the solubility is a significant property required forthe reactive dye on carrying out the dyeing or printing of fibermaterials without any difficulty, as already known, for example, from"The dictionary of dyes and dyeing", edited by K. G. Ponting, page 159(1980). Moreover, dyeing and printing systems in a dye house have beenactivity mechanized and automated in many aspects for saving energy andlabor, and therefore the reactive dyes have been eagerly required to beformed into an aqueous liquid composition for automatic weighing anddispensing systems. Also for this reason, the solubility of the reactivedye is significant.

Generally speaking, a reactive dye having a high solubility decreasesits affinity to fibers, and is easy to hydrolyze its fiber reactivegroup, resulting in decrease of its build-up property.

Therefore, it is considered that the solubility of the reactive dye canbe improved with detriment to the build-up property and vice versa.

The build-up property is significant from economical point of view, andtherefore now strongly desired to be improved.

In order to meet needs of high level for fastness properties of the dyedproducts, it is required to make a molecular structure of the dye and abonding strength between the dye and fibers stable under certainconditions of dyeing procedures and after treatments and usingconditions of the dyed products.

The present inventors have undertaken extensive studies to improve thedefects of the above known reactive dyes and to find reactive dyes of ared color meeting various needs of high level including those describedabove, and as a result have found a specific monoazo compound.

The present invention provides a monoazo compound represented by thefollowing formula (I) in the free acid form, ##STR4## wherein D isunsubstituted or substituted phenylene or naphthylene, R is hydrogen orunsubstituted or substituted alkyl, A is unsubstituted or substitutedphenylene or naphthylene, Z₁ and Z₂ independently of one another areeach --SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Y in which Y is a group splittable bythe action of an alkali, and X is unsubstituted or substituted pyridinioor amino of the following formula (II), ##STR5## in which R₁ and R₂independently of one another are each hydrogen or unsubstituted orsubstituted alkyl, phenyl, naphthyl or benzyl, provided that when anyone of R₁ and R₂ is hydrogen and the other is phenyl, the phenyl is onemember selected from phenyl and mono- or di-sulfophenyl which areunsubstituted or substituted by a substituent in which the atom attachedto the carbon atom of the phenyl is one other than oxygen, sulfur andnitrogen, with the proviso that Z₁ is located at m- or p-position to theazo group when D is phenylene.

The present invention further provides a process for producing themonoazo compound of the above formula (I), which comprises (1) reactinga monoazo intermediate compound represented by the following formula(VII) in the free acid form, ##STR6## wherein D and Z₁ are as definedabove, an aromatic amine compound represented by the following formula(VIII). ##STR7## wherein R, A and Z₂ are as defined above, and any oneof an amine compound represented by the following formula (IX), ##STR8##wherein R₁ and R₂ are as defined above, or a pyridine compoundrepresented by the following formula (X), ##STR9## wherein R₈ ishydrogen, carboxy, carbamoyl, sulfo, halogeno or unsubstituted orsubstituted alkyl, with a cyanuric halide in an optional order to obtainthe monoazo compound of the formula (I), or (2) reacting the aromaticamine compound of the formula (VIII) any one of the amine compound ofthe formula (IX) or the pyridine compound of the formula (X), and anaphthalenedisulfonic acid of the following formula (XI) in the freeacid form, ##STR10## with a cyanuric halide in an optional order,followed by coupling with a diazonium salt of another aromatic aminecompound of the following formula (XII),

    Z.sub.1 --D--NH.sub.2 (XII)

wherein Z₁ and D are as defined above, to obtain the monoazo compound ofthe formula (I).

The present invention furthermore provides a process for dyeing orprinting fiber materials, which comprises using the monoazo compound ofthe formula (I).

In the present invention, the phenylene represented by D in the aboveformula (I) may be unsubstituted or substituted once, twice or threetimes by methyl, ethyl, methoxy, ethoxy, halogeno, acetylamino,propionylamino, nitro, sulfo, carboxy, vinylsulfonyl orβ-sulfatoethylsulfonyl. Of these, preferred are those substituted twiceor less. Particularly preferred is sulfophenylene from viewpoint of dyeperformances.

The naphthylene represented by D may be unsubstituted or substitutedonce or twice by sulfo, vinylsulfonyl or β-sulfatoethylsulfonyl. Ofthese, preferred are those once substituted. Particularly preferred issulfonaphthylene from viewpoint of dye performances.

Among those represented by D, particularly preferred are thoserepresented by the following formulas, ##STR11## wherein the linkageasterisked bonds to the azo group.

The alkyl represented by R is preferably one having 1 to 4 carbon atoms,and may be unsubstituted or substituted by hydroxy, cyano, alkoxy having1 to 4 carbon atoms, halogeno, carboxy, carbamoyl, C₁ -C₄alkoxycarbonyl, C₁ -C₄ alkylcarbonyloxy, sulfo or sulfamoyl. Examples ofthe alkyl are methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl,3,4-dihydroxybutyl, cyanomethyl, 2-cyanoethyl, 3-cyanopropyl,methoxymethyl, ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl,3-methoxypyropyl, 3-ethoxypropyl, 2-hydroxy-3-methoxypropyl,chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl,3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl,2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl,carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, 2-methoxycarbonylethyl,2-ethoxycarbonylethyl, 3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl,4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl,ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl,2-ethylcarbonyloxyethyl, 3-methylcarbonyloxypropyl,3-ethylcarbonyloxypropyl, 4 -methylcarbonyloxybutyl,4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl,4-sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl,4-sulfamoylbutyl and the like.

Among those represented by R, preferred are hydrogen, methyl and ethyl.

The phenylene represented by A may be unsubstituted or substituted onceor twice by methyl, ethyl, methoxy, ethoxy, chloro, bromo or sulfo, andthe naphthylene represented by A may be unsubstituted or substituted bysulfo. Preferred examples thereof are as follows: ##STR12##

In the above formulas, the linkage asterisked bonds to the group of##STR13##

The group Y splittable by the action of an alkali in --SO₂ CH₂ CH₂ Yrepresented by Z₁ and Z₂ includes, for example, OSO₃ H, OPO₃ H, OCOCH₃,SOO₃ H, Cl and the like. Among those represented by Z₁ and Z₂, preferredare --SO₂ CH₂ CH₂ OSO₃ H and --SO₂ CH═CH₂.

When X is the amino represented by the formula (II), the alkylrepresented by R₁ and R₂ is preferably one having 1 to 4 carbon atoms,and may be unsubstituted or substituted once or twice by alkoxy having 1to 4 carbon atoms, sulfo, carboxy, hydroxy, chloro, phenyl or sulfato.Among those, preferred are methyl, ethyl, n-propyl, iso-propyl, n-butyl,iso-butyl, sec-butyl, β-hydroxyethyl, β-sulfatoethyl, β-sulfoethyl,β-methoxyethyl, β-carboxyethyl and the like.

The phenyl represented by R₁ and R₂ may be unsubstituted or substitutedonce or twice by alkyl having 1 to 4 carbon atoms, sulfo, carboxy orchloro. Of these, particularly preferred are phenyl, 2-, 3- or4-sulfophenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-chlorophenyl,3,4-, 3,5- or 3,6-disulfophenyl, 2-, 3- or 4-methylphenyl and the like.

The naphthyl represented by R₁ and R₂ may be unsubstituted orsubstituted once, twice or three times by hydroxy, carboxy, sulfo, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or chloro.Of these, particularly preferred are 2-, 3-, 4-, 5-, 6-, 7- or8-sulfo-1-naphthyl, 1-, 5-, 6-, 7- or 8-sulfo-2-naphthyl, 5,7-, 6,8-,4,8-, 4,7-, 3,8-, 4,6-, 3,7- or 3,6-disulfo-2-naphthyl, 4,6,8-, 2,4,7-or 3,6,8-trisulfo-1-naphthyl, 1,5,7-, 4,6,8- or3,6,8-trisulfo-2-naphthyl and the like.

The benzyl represented by R₁ and R₂ may be unsubstituted or substitutedonce or twice by alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4carbon atoms, sulfo or chloro. Of these, particularly preferred arebenzyl, 2-, 3- or 4-sulfobenzyl.

In the present invention, preferred is a case where any one of R₁ and R₂is methyl or ethyl, and the other is phenyl unsubstituted or substitutedby alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms,sulfo, carboxy or halogeno, and any one of R₁ and R₂ is hydrogen, andthe other is phenyl or mono- or di-sulfophenyl unsubstituted orsubstituted by a substituent in which the atom attached to the carbonatom of the phenyl is one other than oxygen, sulfur and nitrogen. Suchsubstituent includes, for example, alkyl having 1 to 4 carbon atoms,carboxy and halogeno.

When X is pyridinio, the pyridinio may be unsubstituted or substitutedby carboxy, carbamoyl, sulfo, halogeno or unsubstituted or substitutedalkyl having 1 to 4 carbon atoms, such as β-hydroxyethyl, β-sulfoethyland the like. Of these, preferred are carboxypyridinio andcarbamoylpyridinio. Particularly preferred from viewpoint of dyeperformances is carboxypyridinio.

The monoazo compound represented by the formula (I) may be in the formof free acid or preferably in the form of alkali metal or alkaline earthmetal salt such as sodium salt, potassium salt and the like.

Among the monoazo compounds of the formula (I), preferred is onerepresented by the following formula (XIII) in the free acid form,##STR14## wherein R, A, X, Z₁ and Z₂ are as defined above.

Of these, particularly preferred are those represented by the followingformulas (IV), (V) and (VI) in their free acid form, the formula (IV)being ##STR15## wherein R, Z₁ and Z₂ are as defined above, R₃ ishydrogen, methyl or ethyl, and R₄ is hydrogen, methyl, ethyl, sulfo orchloro, the formula (V) being ##STR16## wherein R, Z₁ and Z₂ are asdefined above, R₅ is hydrogen, methyl or ethyl, and R₆ is hydrogen,methyl, ethyl, sulfo or chloro, and the formula (VI) being ##STR17##wherein R, Z₁ and Z₂ are as defined above, and R₇ is hydrogen, carboxyor carbamoyl.

The monoazo compound of the formula (I) can be produced in a mannerexemplified as follows.

Any one of the monoazo intermediate compound of the formula (VII) or thearomatic amine compound of the formula (VIII) is subjected to firstcondensation with a cyanuric halide such as cyanuric chloride andcyanuric fluoride, followed by second condensation using the remainingone, thereby obtaining the corresponding monohalogenotriazine compound.

The first and second condensations can be carried out in an aqueousmedium at a temperature of -10° to 50° C., preferably 0° to 30° C.,while controlling the pH within a range of 1 to 10, preferably 2 to 7,and at a temperature of 0° to 70° C., preferably 10° to 50° C., whilecontrolling the pH within a range of 2 to 9, preferably 3 to 6,respectively.

Successively, the monohalogenotriazine compound is subjected to thirdcondensation with the amine compound of the formula (IX) or the pyridinecompound of the formula (X).

The third condensation can be carried out in an aqueous medium at atemperature of 50° to 100° C., preferably 70° to 100° C., whilecontrolling the pH within a range of 2 to 9, preferably 3 to 7, wherebythe desired monoazo compound of the formula (I) can be produced.

Alternatively, the amine compound (IX) or the pyridine compound (X) canbe subjected to first condensation with the cyanuric halide, followed bysecond and third condensations using the monoazo intermediate compound(VII) and the aromatic amine compound (VIII) in an optional order. Inthis case, the first condensation can be carried out in an aqueousmedium at a temperature of -10° to 50° C., preferably 0° to 30° C.,while controlling the pH within a range of 1 to 10, preferably 2 to 7,the second condensation at a temperature of 0° to 70° C., preferably 10°to 50° C., while controlling the pH within a range of 2 to 9, preferably3 to 6, and the third condensation at a temperature of 50 ° to 100° C.,preferably 50° to 80° C., while controlling the pH within a range of 2to 9, preferably 3 to 7.

In another manner, the naphthalenedisulfonic acid of the formula (XI),namely H acid or K acid, and the aromatic amine compound of the formula(VIII), and the amine compound of the formula (IX) or the pyridinecompound of the formula (X) can be subjected to condensation with thecyanuric halide in an optional order, followed by coupling with adiazonium salt of another aromatic amine compound of the formula (XII),whereby the desired monoazo compound (I) can be also produced.

In the above manners, the order of the condensation is not particularlylimited. However, considering the reaction yield and quality of thedesired monoazo compound of the formula (I), it is favorable to use anyone lower in the reactivity to the cyanuric halide in an earlier stage.

The amine compound (IX) usable in the present invention includes, forexample, ammonia, aromatic amines and aliphatic amines. Examples of thearomatic amines are 1-aminobenzene, 1-amino-2-, 3- or 4-methylbenzene,1-amino-3,4- or 3,5-dimethylbenezene, 1-amino-2-, 3- or 4-ethylbenzene,1-amino-2-, 3- or 4-chlorobenzene, 3- or 4-amino-phenylmethane sulfonicacid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid,3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid,4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid,5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1,4disulfonic acid,4-aminobenzene-1,2-disulfonic acid, 4-aminobenzene-1,2-disulfonic acid,4-amino-5-methylbenzene-1,2-disulfonic acid, 2-, 3- or 4-aminobenzoicacid, 5-aminobenzene-1,3-dicarboxylic acid, N-methylaminobenzene,N-ethylaminobenzene, 1-methylamino-3- or 4-methylbenzene,1-ethylamino-4-chlorobenzene, 1-ethylamino-3- or 4-methylbenzene,1-(2-hydroxyethyl)amino-3-methylbenzene, 3- or 4-methylaminobenzoicacid, 3- or 4-methylaminobenzenesulfonic acid,2-aminonaphthalene-1-sulfonic acid, 4-aminonaphthalene-1-sulfonic acid,5-aminonaphthalene-1-sulfonic acid, 6-aminonaphthalene-1-sulfonic acid,7-aminonaphthalene-1-sulfonic acid, 8-aminonaphthalene-1-sulfonic acid,1-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-2-sulfonic acid,5-aminonaphthalene-2sulfonic acid, 6-aminonaphthalene-2-sulfonic acid,7-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonicacid, 7-ethylaminonaphthalene-2-sulfonic acid,7-butylaminonaphthalene-2-sulfonic acid,7-isobutylaminonaphthalene-2-sulfonic acid,8-aminonaphthalene-2-sulfonic acid, 4-aminonaphthalene-1,3disulfonicacid, 5-aminonaphthalene-1,3-disulfonic acid,6-aminonaphthalene-1,3-disulfonic acid,7-aminonaphthalene-1,3-disulfonic acid,8-aminonaphthalene-1,3-disulfonic acid,2-aminonaphthalene-1,5-disulfonic acid,3-aminonaphthalene-1,5-disulfonic acid,4-aminonaphthalene-1,5-disulfonic acid,4-aminonaphthalene-1,6-disulfonic acid,8-aminonaphthalene-1,6-disulfonic acid,4-aminonaphthalene-1,7-disulfonic acid,3-aminonaphthalene-2,6-disulfonic acid,4-aminonaphthalene-2,6-disulfonic acid,3-aminonaphthalene-2,7-disulfonic acid, 4-aminonaphthalene-2,7-disulfonic acid, 6-aminonaphthalene-1,3,5-trisulfonic acid,7-aminonaphthalene-1,3,5-trisulfonic acid,4-aminonaphthalene-1,3,6-trisulfonic acid,7-aminonaphthalene-1,3,6-trisulfonic acid,8-aminonaphthalene-1,3,6-trisulfonic acid,4-aminonaphthalene-1,3,7-trisulfonic acid and the like.

Examples of the aliphatic amines are methylamine, ethylamine,n-propylamine, isopropylamine, n-butylamine, isobutylamine,sec-butylamine, dimethylamine, diethylamine, methylethylamine,allylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol,2-methylaminoethanol, bis-(2-hydroxyethyl)-amine,2-acetylaminoethylamine, 1-amino-2-propanol, 3-methoxypropylamine,1-amino-3-dimethylaminopropane, 2-aminoethanesulfonic acid,aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid,3-amino-1-propanesulfonic acid, 2-sulfatoethylamine, aminoacetic acid,methylaminoacetic acid, ε-aminocaproic acid, benzylamine, 2-, 3- or4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine,1-phenyl-2-propylamine and the like.

Of these, preferred examples are aniline, N-methylaniline,N-ethylaniline, 2-, 3- or 4-chloroaniline, N-methyl-2-, 3- or4-chloroaniline, N-ethyl-2-, 3- or 4-chloroaniline, 2-, 3- or4-methylaniline, 3- or 4-methylaminobenzenesulfonic acid, 3- or4-ethylaminobenzenesulfonic acid, taurine, N-methyltaurine, mono- ordi-ethanolamine and the like.

Examples of the pyridine compound (X) usable in the present inventionare pyridine, 2-, 3- or 4-carboxypyridine, 2-, 3- or4-carbamoylpyridine, 3-sulfopyridine, 4-β-sulfoethylpyridine,3-β-hydroxyethylpyridine, 4-chloropyridine, 3-methylpyridine,3,5-dicarboxypyridine and the like. Of these, particularly preferred are3- or 4-carboxypyridine (nicotinic acid, isonicotinic acid) and thelike.

After completion of the reactions, the desired monoazocompound-containing reaction mixture may be subjected to salting-out ina conventional manner, demineralization with a semipermeable membrane,evaporation such as spray-drying or the like, if desired, with use ofusual auxiliary agents such as stabilizing agents, dyeing improvers andthe like, to provide a pulverulent or liquid commercial product.

The monoazo compound of the present invention is fiber-reactive anduseful for dyeing or printing hydroxyl group-containing and amidegroup-containing mateials. The materials are favorably in a fibrousform.

The hydroxyl group-containing materials include natural or synthetichydroxyl group-containing materials such as cellulose fiber materials,regenerated products thereof and polyvinyl alcohol. Examples of thecellulose fiber materials are cotton and other vegetable fibers such aslinen, hemp, jute and ramie fibers. Examples of the regeneratedcellulose fibers are viscose staple and filament viscose.

The amide group-containing materials include synthetic or naturalpolyamide and polyurethane. Examples of the materials, particularly inthe fibrous forms, are wool and other animal furs, silk, leather,polyamide-6,6, polyamide-6, polyamide-11 and polyamide-4.

The dyeing may be carried out in a suitable manner, which can beselected from conventional manners depending on the physical andchemical properties of said fiber materials.

For example, cellulose fiber materials can be dyed using the monoazocompound by an exhaustion dyeing, padding including cold batch-up dyeingor printing method.

The exhaustion dyeing can be carried out at a relatively low temperaturein the presence of an acid binding agent such as sodium carbonate,trisodium phosphate, sodium hydroxide and the like, if desired, using aneutral salt such as sodium sulfate, sodium chloride and the like,together with a hydrotropic agent, a penetrant or a level dyeing agent.The neutral salt suitable for promoting the exhaustion may be added to adye bath before or after temperature reaching a desired level for thedyeing, if desired, dividedly.

The padding can be carried out by padding the fiber materials at ambinettemperature or an elevated temperature, and after drying, steaming ordry-heating the materials to perform the dye-fixation.

The cold batch-up dyeing can be carried out by padding the fibermaterials with a padding liquor at ambient temperature, batching up andallowing them to stand on a roller for 3 hours or more or over night,followed by washing with water and drying.

The printing can be carried out in a one-phase or two-phase manner. Theone-phase printing may be conducted by printing the fiber materials witha printing paste containing an acid binding agent such as sodiumhydrogencarbonate and the like, followed by steaming at a temperature of100° to 160° C. The two-phase printing may be conducted by printing thefiber materials with a neutral or weakly acidic printing paste, andpassing the materials through a hot alkaline bath containing anelectrolyte or over-padding the materials with an alkaline paddingliquor containing an electrolyte, followed by a steaming or dry-heatingtreatment.

For the preparation of the printing paste, a paste or emulsifier such assodium alginate, starch ether and the like may be used, if desired,together with a conventional auxiliary agent such as urea and/ordispersing agent.

The acid binding agent useful for fixing the compound of the presentinvention on the cellulose fiber materials includes water-soluble basicsalts consisting of alkali or alkaline earth metals and inorganic ororganic acids or compounds capable of liberating alkalis under heatingconditions. Preferred are alkali metal hydroxides and alkali metal saltsof inorganic or organic acids having a weak or medium strength.Particularly preferred are sodium salts and potassium salts. Examplesthereof are sodium hydroxide, potassium hydroxide, sodiumhydrogencarbonate, sodium carbonate, sodium formate, potassiumcarbonate, sodium dihydrogenphosphate, disodium hydrogenphosphate,trisodium phosphate, sodium silicate, sodium trichloroacetate and thelike.

The dyeing of natural or synthetic polyamide and polyurethane fibermaterials can be carried out by performing exhaustion in an acid or weakacid bath, while controlling the pH value, and then making the bathneutral, or in some cases alkaline to perform the fixation. The dyeingtemperature ranges usually from 60° to 120° C. In order to achieve alevel dyeing, there may be used a conventional level dyeing agent suchas condensation product between cyanuric chloride and 3 times by mole ofaminobenzenesulfonic acid or aminonaphthalenesulfonic acid, or anaddition product between stearylamine and ethylene oxide, and the like.

The present monoazo compound can be characterized by excellent dyeperformance in the dyeing and printing of fiber materials, particularlycellulose fiber materials. For example, the compound can give a dyedproduct excellent in light fastness, perspiration-light fastness,formalin fastness, wet fastness such as washing resistance,peroxide-washing resistance, chlorine resistance, chlorine bleachingresistance, perspiration resistance and acid-hydrolysis resistance, andalkali fastness, abrasion fastness and iron fastness. The monoazocompound can also exhibit extremely excellent build-up, level-dyeing andwashing-off properties and high solubility as well as high exhaustionand fixation percentages. Moreover, when used for the dyeing orprinting, the monoazo compound can hardly be affected by changes indyebath conditions such as temperatures, pH, amounts of inorganic saltsand bath ratio, so that a dyed or printed product with a constantquality can be obtained with superior reproducibility.

Further, particularly when applied for the dyeing by the cold batch-updyeing method, the monoazo compound can exhibit excellent build-upproperty and alkali stability (almost no hydrolysis by the action of thealkali agent) and almost no difference in the depth and shade appearsbetween the dyed products obtained by fixing at 25° C. and at a lowertemperature than that.

The present invention is illustrated in more detail with reference tothe following Examples, which are only illustrative, but not limitative.In Examples, all parts and % are by weight.

EXAMPLE 1

1-Amino-8-naphthol-3,6-disulfonic acid (319.3 parts) was subjected tofirst condensation with cyanuric chloride (184.5 parts), followed bysecond condensation with 1-aminobenzene-3-β-sulfatoethylsulfone (281.3parts), thereby obtaining a monochlorotriazinyl compound represented bythe following formula in the free acid form. ##STR18##

On the other hand, 1-amino-2-sulfobenzene-4-β-sulfatoethylsulfone (361.3parts) was diazotized in a conventional manner, and the resultingdiazonium compound was subjected to coupling with themonochlorotriazinyl compound obtained above, followed by condensationwith aniline (93.1 parts). The reaction mixture was mixed with sodiumchloride to precipitate crystals, which were separated on a filter.Thus, there was obtained a monoazo compound represented by the followingformula in the free acid form. ##STR19##

EXAMPLE 2

Example 1 was repeated, provided that the following diazo component,coupler, amine and reactive component shown in the 2nd, 3rd, 4th and 5thcolumns of the following Table I, respectively, were used in place of1-amino-2-sulfobenzene-4-β-sulfatoethylsulfone,1-amino-8-naphthol-3,6-disulfonic acid, aniline and1-aminobenzene-3-β-sulfatoethylsulfone used in Example 1, respectively,thereby obtaining the corresponding monoazo compound, which showed eachcolor shown in 6th column of the following Table I on the dyeing ofcellulose fiber materials.

                                      TABLE I                                     __________________________________________________________________________    Run                                                                              2        3       4         5         6                                     No.                                                                              Diazo component                                                                        Coupler Amine     Reactive component                                                                      Color                                 __________________________________________________________________________    1  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Aniline   1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     vinylsulfone                                       sulfatoethyl-                                                                          disulfonic acid                                                      sulfone                                                                    2  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Aniline   1-Aminobenzene-4-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    3  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            N-Ethylaniline                                                                          1-Aminobenzene-4-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    4  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            N-Ethyl-p-                                                                              1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         chloroaniline                                                                           β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    5  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            p-Chloroaniline                                                                         1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    6  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Taurine   2-Aminonaphtha-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-     lene-6-β-sulfato-                             sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone                    sulfonic acid                                   7  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            β-Hydroxyethyl-                                                                    1-Ethylamino-                                                                           Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         amine     benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone                    sulfone                                         8  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            2-Aminonaphtha-                                                                         1-Amino-2-sulfo-                                                                        Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         lene-6-sulfonic                                                                         benzene-4-β -                                 sulfatoethyl-                                                                          disulfonic acid                                                                       acid      sulfatoethyl-                                      sulfone                    sulfone                                         9  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Benzylamine                                                                             1-Amino-2-sulfo-                                                                        Red                                      benzene-4-β-                                                                      naphthol-3,6-     benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone                    sulfone                                         10 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            N-Ethylaniline                                                                          2-Aminonaphtha-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         3-sulfonic acid                                                                         lene-8-β-sulfato-                             sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-6-                                    sulfone                    sulfonic acid                                   11 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            N-Methylaniline                                                                         2-Aminonaphtha-                                                                         Yellow-                                  benzene-4-β-                                                                      naphthol-4,6-     lene-5-β-sulfato-                                                                  ish red                                  sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone                    sulfonic acid                                   12 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            o-Methylaniline                                                                         1-Amino-2-                                                                              Yellow-                                  benzene-4-β-                                                                      naphthol-4,6-     methoxybenzene-                                                                         ish red                                  sulfatoethyl-                                                                          disulfonic acid   5-β-phosphato-                                sulfone                    ethylsulfone                                    13 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Aniline   1-Aminobenzene-                                                                         Yellow-                                  benzene-5-β-                                                                      naphthol-3,6-     3-β-sulfatoethyl-                                                                  ish red                                  sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    14 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            N-Ethylaniline                                                                          2-Aminonaphtha-                                                                         Yellow-                                  benzene-5-β-                                                                      naphthol-3,6-     lene-6-β-sulfato-                                                                  ish red                                  sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone                    sulfonic acid                                   15 2-Aminonaphta-                                                                         1-Amino-8-                                                                            N-Ethylaniline                                                                          2-Aminonaphtha-                                                                         Bluish                                   lene-5-β-sulfato-                                                                 naphthol-3,6-     lene-6-β-sulfato-                                                                  red                                      ethylsulfone-1-                                                                        disulfonic acid   ethylsulfone-1-                                    sulfonic acid              sulfonic acid                                   16 2-Aminonaphta-                                                                         1-Amino-8-                                                                            N-Ethyl-p-chloro-                                                                       1-Aminobenzene-                                                                         Bluish                                   lene-5-β -sulfato-                                                                naphthol-3,6-                                                                         aniline   3-β-sulfatoethyl-                                                                  red                                      ethylsulfone-1-                                                                        disulfonic acid   sulfone                                            sulfonic acid                                                              17 2-Aminonaphta-                                                                         1-Amino-8-                                                                            o-Chloroaniline                                                                         1-Ethylamino-                                                                           Bluish                                   lene-5-β-sulfato-                                                                 naphthol-3,6-     benzene-3-β-                                                                       red                                      ethylsulfone-1-                                                                        disulfonic acid   sulfatoethyl-                                      sulfonic acid              sulfone                                         18 2-Aminonaphta-                                                                         1-Amino-8-                                                                            N-Methyltauriue                                                                         1-Amino-2-                                                                              Bluish                                   lene-5-β-sulfato-                                                                 naphthol-3,6-     methoxy-5-methyl-                                                                       red                                      ethylsulfone-1-                                                                        disulfonic acid   benzene-4-β-                                  sulfonic acid              sulfatoethyl-                                                                 sulfone                                         19 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline   1-Aminobenzene-3-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              20 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Methylaniline                                                                         1-Aminobenzene-3-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              21 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Ethyl-p-                                                                              2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         chloroaniline                                                                           lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone-1-                 sulfonic acid                                      sulfonic acid                                                              22 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Taurine   2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone-1-                 sulfonic acid                                      sulfonic acid                                                              23 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Dihydroxyethyl-                                                                         1-Amino-2-chloro-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         amine     benzene-5-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              24 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Ethylamine                                                                              1-Amino-2-ethoxy-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-     benzene-5-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              25 1-Aminobenzene                                                                         1-Amino-8-                                                                            Ethylamine                                                                              1-Amino-2-ethoxy-                                                                       Red                                      2,5-bis(β-                                                                        naphthol-4,6-     benzene-5-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone)                   sulfone                                         26 2-Aminonaphth-                                                                         1-Amino-8-                                                                            Aniline   1-N-Ethylamino-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              27 2-Aminonaphth-                                                                         1-Amino-8-                                                                            N-Methylaniline                                                                         1-Aminobenzene-4-                                                                       Bluish                                   lene-5-β-                                                                         naphthol-3,6-     β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              28 2-Aminonaphth-                                                                         1-Amino-8-                                                                            m-Sulfoaniline                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              29 2-Aminonaphth-                                                                         1-Amino-8-                                                                            m-Sulfoaniline                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              30 2-Aminonaphth-                                                                         1-Amino-8-                                                                            Aniline   1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              31 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            p-Methylaniline                                                                         1-Aminobenzene-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-     3-β-sulfatoethyl-                             sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              32 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            p-Methylaniline                                                                         1-N-Ethylamino-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-     benzene-3-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              33 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            p-Chloroaniline                                                                         1-N-Ethylamino-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-     benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              34 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Ethylaniline                                                                          1-Aminobenzene-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-     3-β-sulfatoethyl-                             sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              35 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline-3,5-                                                                            1-Aminobenzene-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-                                                                         disulfonic acid                                                                         3-β-sulfatoethyl-                             sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              36 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline-4-                                                                              1-Aminobenzene-4-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-                                                                         sulfonic acid                                                                           β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              37 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Methyl-p-                                                                             1-Aminobenzene-4-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-                                                                         toluidine β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              38 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Ethylaniline-                                                                         1-Aminobenzene-4-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         4-carboxylic acid                                                                       β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              39 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline-4-                                                                              1-N-β-Hydroxy-                                                                     Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         carboxylic acid                                                                         ethylamino-                                                                             red                                      sulfatoethyl-                                                                          disulfonic acid   benzene-3-β-                                  sulfone-1-                 sulfatoethyl-                                      sulfonic acid              sulfone                                         40 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-Ethylaniline                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     3-β-chloroethyl-                                                                   red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1,7-                                                                  disulfonic acid                                                            41 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            N-Ethylaniline                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     3-β-chloroethyl-                                                                   red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1,7-                                                                  disulfonic acid                                                            42 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-Bromo-N-Methyl-                                                                       1-Aminobenzene-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         aniline   3-β-chloroethyl-                                                                   red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    disulfonic acid                                                            43 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline   1-N-β-Carbamoyl-                                                                   Bluish                                   lene-6-β-                                                                         naphthol-3,6-     ethylaminobenzene-                                                                      red                                      sulfatoethyl-                                                                          disulfonic acid   3-β-sulfatoethyl-                             sulfone-1-                 sulfone                                            disulfonic acid                                                            44 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline   1-N-Propylamino-                                                                        Bluish                                   lene-6-β-                                                                         naphthol-3,6-     benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            disulfonic acid                                                            45 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Aniline   1-N-β-Carboxy-                                                                     Bluish                                   lene-6-β-                                                                         naphthol-3,6-     ethylamino-                                                                             red                                      sulfatoethyl-                                                                          disulfonic acid   benzene-4-β-                                  sulfone-1-                 sulfatoethyl-                                      disulfonic acid            sulfone                                         46 1-Aminobenzene-                                                                        1-Amino-8-                                                                            p-Chloroaniline                                                                         1-N-β -Methoxy-                                                                    Red                                      4-β-sulfato-                                                                      naphthol-3,6-     ethylamino-                                        ethylsulfone-2-                                                                        disulfonic acid   benzene-3-β-                                  sulfonic acid              sulfatoethyl-                                                                 sulfone                                         47 1-Aminobenzene-                                                                        1-Amino-8-                                                                            Aniline   2-Aminonaphtha-                                                                         Red                                      4-β-sulfato-                                                                      naphthol-3,6-     lene-8-β-sulfato-                             ethylsulfone-2-                                                                        disulfonic acid   ethylsulfone                                       sulfonic acid                                                              48 1-Aminobenzene-                                                                        1-Amino-8-                                                                            Aniline   2-Aminonaphtha-                                                                         Red                                      4-β-sulfato-                                                                      naphthol-3,6-     lene-5-β-sulfato-                             ethylsulfone-2-                                                                        disulfonic acid   ethylsulfone                                       sulfonic acid                                                              49 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-Methylaniline                                                                         1-N-Ethylamino-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            disulfonic acid                                                            50 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            p-Chloroaniline                                                                         1-N-Ethylamino-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            disulfonic acid                                                            51 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            2-Methylaniline                                                                         1-Aminobenzene-3-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    disulfonic acid                                                            52 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            2,4-Dimethyl-                                                                           1-Aminobenzene-3-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-                                                                         aniline   β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    disulfonic acid                                                            53 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-Ethylaniline                                                                          1-Aminobenzene-3-                                                                       Red                                      lene-6-β-                                                                         naphthol-4,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    disulfonic acid                                                            __________________________________________________________________________

EXAMPLE 3

1-Amino-8-naphthol-3,6-disulfonic acid (319.3 part) was subjected tofirst condensation with cyanuric chloride (184.5 parts), followed bysecond condensation with 1-aminobenzene-3-β-sulfatoethylsulfone (281.3parts) whereby obtaining a monochlorotriazinyl compound of the followingformula in the free acid form. ##STR20##

On the other hand, 1-amino-2-sulfobenzene-4-β-sulfatoethylsulfone (361.3parts) was diazotized in a conventional manner, and the resultingdiazonium compound was subjected to coupling with themonochlorotriazinyl compound obtained above, followed by condensationwith nicotinic acid (123 parts). The reaction mixture was mixed withsodium chloride to precipitate crystals, which were separated on afilter.

There was obtained a monoazo compound represented by the followingformula in the free acid form. ##STR21##

EXAMPLE 4

Example 3 was repeated, provided that the following diazo component,coupler, pyridine compound and reactive component shown in 2nd, 3rd, 4thand 5th columns of the following Table II, respectively, were used inplace of 1-amino-2-sulfobenzene-4-β-sulfatoethylsulfone,1-amino-8-naphthol-3,6-disulfonic acid, nicotinic acid and1-aminobenzene-3-β-sulfatoethylsulfone, respectively, thereby obtainingthe corresponding monoazo compound, which showed the color shown in 6thcolumn of the following Table II on the dyeing of cellulose fibermaterials.

                                      TABLE II                                    __________________________________________________________________________    Run                                                                              2        3       4         5         6                                     No.                                                                              Diazo component                                                                        Coupler Pyridine compound                                                                       Reactive component                                                                      Color                                 __________________________________________________________________________    1  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     vinylsulfone                                       sulfatoethyl-                                                                          disulfonic acid                                                      sulfone                                                                    2  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Isonicotinic                                                                            1-Aminobenzene-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         acid      4-β-sulfatoethyl-                             sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    3  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinamide                                                                            1-Aminobenzene-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-     4-β-sulfatoethyl-                             sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    4  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            3-Sulfopyridine                                                                         1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-     β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    5  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            4-β-Hydroxy-                                                                       1-Aminobenzene-3-                                                                       Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         ethylpyridine                                                                           β-sulfatoethyl-                               sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone                                                                    6  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminonaphtha-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-     lene-6-β-sulfato-                             sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone                    sulfonic acid                                   7  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            4-β-Sulfoethyl-                                                                    1-Ethylamino-                                                                           Red                                      benzene-4-β-                                                                      naphthol-3,6-                                                                         pyridine  benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone                    sulfone                                         8  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          1-Amino-2-sulfo-                                                                        Red                                      benzene-4-β-                                                                      naphthol-3,6-     benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone                    sulfone                                         9  1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Pyridine  1-Amino-2-sulfo-                                                                        Red                                      benzene-4-β-                                                                      naphthol-3,6-     benzene-4-β-                                  sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone                    sulfone                                         10 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Red                                      benzene-4-β-                                                                      naphthol-3,6-     lene-8-β-sulfato-                             sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-6-                                    sulfone                    sulfonic acid                                   11 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            4-Chloropyridine                                                                        2-Aminonaphtha-                                                                         Yellow-                                  benzene-4-β-                                                                      naphthol-4,6-     lene-5-β-sulfato-                                                                  ish red                                  sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone                    sulfonic acid                                   12 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            3-Methylpyridine                                                                        1-Amino-2-methoxy-                                                                      Yellow-                                  benzene-4-β-                                                                      naphthol-4,6-     benzene-5-β-                                                                       ish red                                  sulfatoethyl-                                                                          disulfonic acid   phosphatoethyl-                                    sulfone                    sulfone                                         13 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Yellow-                                  benzene-5-β-                                                                      naphthol-3,6-     3-β-sulfato-                                                                       ish red                                  sulfatoethyl-                                                                          disulfonic        ethylsulfone                                       sulfone  acid                                                              14 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Isonicotinamide                                                                         2-Aminonaphtha-                                                                         Yellow-                                  benzene-5-β-                                                                      naphthol-3,6-     lene-6-β-sulfato-                                                                  ish red                                  sulfatoethyl-                                                                          disulfonic        ethylsulfone-1-                                    sulfone  acid              sulfonic acid                                   15 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic        ethylsulfone-1-                                    sulfone-1-                                                                             acid              sulfonic acid                                      sulfonic acid                                                              16 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     3-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic        sulfone                                            sulfone-1-                                                                             acid                                                                 sulfonic acid                                                              17 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Isonicotinic                                                                            1-Ethylamino-                                                                           Bluish                                   lene-5-β-                                                                         naphthol-3,6-                                                                         acid      benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic        sulfatoethyl-                                      sulfone-1-                                                                             acid              sulfone                                            sulfonic acid                                                              18 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Isonicotinic                                                                            1-Amino-2-methoxy-                                                                      Bluish                                   lene-5-β-                                                                         naphthol-3,6-                                                                         acid      5-methylbenzene-                                                                        red                                      sulfatoethyl-                                                                          disulfonic        4-β-sulfatoethyl-                             sulfone-1-                                                                             acid              sulfone                                            sulfonic acid                                                              19 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     3-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic        sulfone                                            sulfone-1-                                                                             acid                                                                 sulfonic acid                                                              20 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinamide                                                                            1-Aminobenzene-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     3-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic        sulfone                                            sulfone-1-                                                                             acid                                                                 sulfonic acid                                                              21 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone-1-                 sulfonic acid                                      sulfonic acid                                                              22 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-β-Sulfoethyl-                                                                    2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-                                                                         pyridine  lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone-1-                 sulfonic acid                                      sulfonic acid                                                              23 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            4-Chloropyridine                                                                        1-Amino-2-chloro-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     benzene-5-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              24 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            3-Ethylpyridine                                                                         1-Amino-2-ethoxy-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-4,6-     benzene-5-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              25 1-Amino-2-sulfo-                                                                       1-Amino-8-                                                                            Nicotinic acid                                                                          1-Amino-2-ethoxy-                                                                       Bluish                                   benzene-4,5-bis                                                                        naphthol-4,6-     benzene-5-β-                                                                       red                                      (β-sulfatoethyl-                                                                  disulfonic acid   sulfatoethyl-                                      sulfone)                   sulfone                                         26 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     4-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              27 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              28 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-6-β-sulfato-                                                                 naphthol-3,6-     4-β-sulfatoethyl-                                                                  red                                      ethylsulfone-1-                                                                        disulfonic acid   sulfone                                            sulfonic acid                                                              29 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-sulfato-                                                                 naphthol-3,6-     benzene-3-β-                                                                       red                                      ethylsulfone-1-                                                                        disulfonic acid   sulfatoethylsulfone                                sulfonic acid                                                              30 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-sulfato-                                                                 naphthol-3,6-     benzene-4-β-                                                                       red                                      ethylsulfone-1-                                                                        disulfonic acid   sulfatoethyl-                                      sulfonic acid              sulfone                                         31 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-4,6-     3-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              32 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-4-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-4,6-     β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              33 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-4,6-     sulfatoethyl-                                                                           red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              34 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Ethylamino-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-4,6-     benzene-4-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              35 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-4,6-     lene-6-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone-1-                                    sulfone-1-                 sulfonic acid                                      sulfonic acid                                                              36 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-3-                                                                       Bluish                                   lene-5-β-                                                                         naphthol-3,6-     β-sulfatoethyl-                                                                    red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1,7-di-                                                               sulfonic acid                                                              37 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-                                                                         Bluish                                   lene-5-β-                                                                         naphthol-3,6-     4-β-sulfatoethyl-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1,7-di-                                                               sulfonic acid                                                              38 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Propylamino-                                                                        Bluish                                   lene-6-β-                                                                         naphthol-3,6-     benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              39 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-3-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     β-chloroethyl-                                                                     red                                      sulfatoethyl-                                                                          disulfonic acid   sulfone                                            sulfone-1-                                                                    sulfonic acid                                                              40 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Bluish                                   lene-6-β-                                                                         naphthol-3,6-     lene-8-β-sulfato-                                                                  red                                      sulfatoethyl-                                                                          disulfonic acid   ethylsulfone                                       sulfone-1-                                                                    sulfonic acid                                                              41 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-β-Hydroxy-                                                                     Red                                      lene-6-β-                                                                         naphthol-4,6-     ethylaminobenzene-                                 sulfatoethyl-                                                                          disulfonic acid   3-β-sulfatoethyl-                             sulfone-1-                 sulfone                                            sulfonic acid                                                              42 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          2-Aminonaphtha-                                                                         Red                                      lene-6-β-                                                                         naphthol-4,6-     lene-5-β-sulfato-                             sulfatoethyl-                                                                          disulfonic acid   ethylsulfone                                       sulfone-1-                                                                    sulfonic acid                                                              43 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-β-Carbamoyl-                                                                   Bluish                                   lene-6-β-                                                                         naphthol-3,6-     ethylaminobenzene-                                                                      red                                      sulfatoethyl-                                                                          disulfonic acid   3-β-sulfatoethyl-                             sulfone-1-                 sulfone                                            sulfonic acid                                                              44 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-β-Carboxy-                                                                     Bluish                                   lene-6-β-                                                                         naphthol-3,6-     ethylaminobenzene-                                                                      red                                      sulfatoethyl-                                                                          disulfonic acid   4-β-sulfatoethyl-                             sulfone-1-                 sulfone                                            sulfonic acid                                                              45 1-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-N-Methoxyethyl-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     aminobenzene-3-                                                                         red                                      sulfatoethyl-                                                                          disulfonic acid   β-sulfatoethyl-                               sulfone-1-                 sulfone                                            sulfonic acid                                                              46 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Amino-2-methoxy-                                                                      Bluish                                   lene-6-β-                                                                         naphthol-3,6-     5-methylbenzene-                                                                        red                                      sulfatoethyl-                                                                          disulfonic acid   4-β-sulfatoethyl-                             sulfone-1-                 sulfone                                            sulfonic acid                                                              47 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-4-                                                                       Bluish                                   lene-6-β-                                                                         naphthol-3,6-     vinylsulfone                                                                            red                                      sulfatoethyl-                                                                          disulfonic acid                                                      sulfone-1-                                                                    sulfonic acid                                                              48 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene-4-                                                                       Bluish                                   lene-5-β-                                                                         naphthol-3,6-     vinylsulfone                                                                            red                                      sulfatoethyl-                                                                          disulfonic acid                                                      sulfone-1-                                                                    sulfonic acid                                                              49 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Amino-4-methoxy-                                                                      Bluish                                   lene-5-β-                                                                         naphthol-3,6-     benzene-3-β-                                                                       red                                      sulfatoethyl-                                                                          disulfonic acid   sulfatoethyl-                                      sulfone-1-                 sulfone                                            sulfonic acid                                                              50 2-Aminonaphtha-                                                                        1-Amino-8-                                                                            Nicotinic acid                                                                          1-Aminobenzene                                                                          Bluish                                   lene-6-vinyl-                                                                          naphthol-3,6-     4-β-sulfatoethyl-                                                                  red                                      sulfone-1-                                                                             disulfonic acid   sulfone                                            sulfonic acid                                                              __________________________________________________________________________

DYEING EXAMPLE 1

Each of the monoazo compounds obtained in Examples 1 and 3 (0.3 part)was dissolved in water (200 parts), and sodium sulfate (20 parts) andcotton (10 parts) were added thereto. The bath was heated to 50° C.Thirty minutes thereafter, sodium carbonate (4 parts) was added thereto.Dyeing was continued for 1 hour at the temperature. Thereafter, thecotton was washed with water and soaped to obtain each dyed product of adeep red excellent in fastness properties, particularly those such aschlorine fastness, light fastness and perspiration fastness withexcellent build-up property.

DYEING EXAMPLE 2

Each of the monoazo compounds obtained in Examples 1 to 4 (0.3 part) wasdissolved in water (300 parts), and sodium sulfate (30 parts) and cotton(10 parts) were added thereto. The bath was heated to 60° C. Twentyminutes thereafter, sodium carbonate (5 parts) were added thereto.Dyeing was continued for 1 hour at that temperature. Thereafter, thecotton was washed with water and soaped to obtain each dyed product of adeep red color excellent in fastness properties, particularly those suchas chlorine fastness, light fastness and perspiration fastness withexcellent build-up property.

DYEING EXAMPLE 3

    ______________________________________                                        Preparation of dye paste:                                                     ______________________________________                                        Each of the monoazo compounds                                                                          5     parts                                          obtained in Examples 1 to 4                                                   Urea                     5     parts                                          Sodium alginate (50%) stock                                                                            50    parts                                          paste                                                                         Hot water                25    parts                                          Sodium hydrogencarbonate 2     parts                                          Balance (water)          13    parts                                          ______________________________________                                    

Mercerized cotton broad was printed with the dye paste having the abovecomposition, and the printed broad was pre-dried, steamed at 100° C. for5 minutes, washed with hot water, soaped, again washed with water anddried.

Thus, there was obtained each printed product of a red color excellentin fastness properties, particularly those such as chlorine fastness,light fastness and perspiration-light fastness with excellent build-upproperty.

DYEING EXAMPLE 4

Each of the monoazo compounds obtained in Example 1 to 4 (25 parts) wasdissolved in hot water, and the solution was cooled to 25° C. Aqueous32.5% sodium hydroxide solution (5.5 parts) and 50° Be' water glass (150parts) were thereto, and water was added thereto to make the solution1,000 parts at 25° C. Immediately thereafter, cotton cloth was paddedwith the solution, batched up, wrapped tightly with a polyethylene filmand allowed to stand in a room of 20° C. for 20 hours.

On the other hand, a cotton cloth wrapped tightly with a polyethylenefilm, which was prepared in the same manner as above was allowed tostand in a room of 5° C. for 20 hours.

Thereafter, the respective padded cloths were washed with cold water andthen hot water, boil-soaped with a detergent, then washed with coldwater and then dried.

There was observed almost no difference in their color shade and depthbetween the dyed products obtained by standing at 5° C. and 20° C. eachfor 20 hours. In this cold batch-up dyeing method, each of the monoazocompounds was found to have excellent build-up property.

DYEING EXAMPLE 5

Each of the monoazo compounds obtained in Examples 1 to 4 (25 parts) wasdissolved in hot water, and the solution was cooled to 25° C. Aqueous32.5% sodium hydroxide solution (10 parts) and anhydrous sodium sulfate(30 parts) were added thereto, and water was added thereto to make thesolution 1000 parts at 25° C. Immediately thereafter, using the solutionas a padding liquor, viscose rayon woven fabric was subjected topadding, and the padded fabric was batched-up, wrapped tightly with apolyethylene film and allowed to stand in a room of 20° C. for 20 hours.

On the other hand, a viscose rayon woven fabric wrapped tightly with apolyethylene film, which was prepared in the same manner as above, wasallowed to stand in a room of 5° C. for 20 hours.

Thereafter, the respective fabrics were washed with cold water and thenhot water, boil-soaped with a detergent, washed with cold water and thendried.

There was observed almost no difference in their color shade and depthbetween the dyed products obtained by standing at 5° C. and 20° C. eachfor 20 hours.

DYEING EXAMPLE 6

Dyeing Example 2 was repeated, provided that the amount of sodiumcarbonate was changed from 5 parts to 3 parts, whereby the respectivemonoazo compounds gave the dyed products similar to those obtained inDyeing Example 2.

DYEING EXAMPLE 7

Dyeing Example 2 was repeated, provided that the dyeing was carried outat 50° C. in place of 60° C., whereby the respective monoazo compoundsgave the dyed products similar to those obtained in Dyeing Example 2.The dyeing carried out at 70° C. also gave similar results.

DYEING EXAMPLE 8

Dyeing Example 2 was repeated, provided that the amount of sodiumsulfate was changed from 30 parts to 15 parts, whereby the respectivemonoazo compounds gave the dyed products similar to those obtained inDyeing Example 2.

We claim:
 1. A monoazo compound represented by the following formula (I)in the free acid form, ##STR22## wherein D is phenylene which isunsubstituted or substituted once, twice or three times by methyl,ethyl, methoxy, ethoxy, halogeno, acetylamino, propionylamino, nitro,sulfo, carboxy, vinylsulfonyl or β-sulfatoethylsulfonyl, or naphthylenewhich is unsubstituted or substituted once or twice by sulfo,vinylsulfonyl or β-sulfatoethylsulfonyl;R is hydrogen or alkyl which isunsubstituted or substituted by hydroxy, cyano, alkoxy having 1 to 4carbon atoms, halogeno, carboxy, carbamoyl, C₁ -C₄ alkoxycarbonyl, C₁-C₄ alkylcarbonyloxy, sulfo or sulfamoyl; A is phenylene which isunsubstituted or substituted once or twice by methyl, ethyl, methoxy,ethoxy, sulfo, carboxy or halogen, or is napthylene unsubstituted orsubstituted by sulfo; Z₁ and Z₂ independently of one another are each--SO₂ CH═CH₂ or --SO₂ CH₂ CH₂ Y in which Y is a group capable of beingsplit by the action of an alkali; and X is pyridinio which isunsubstituted or substituted by carboxy or carbamoyl, or is amino of thefollowing formula (II): ##STR23## in which any one of R₁ and R₂ ismethyl or ethyl, and the other is phenyl which is unsubstituted orsubstituted once or twice by alkyl having 1 to 4 carbon atoms, sulfo,carboxy, halogeno or alkoxy having 1 to 4 carbon atoms, or any one of R₁and R₂ is hydrogen, and the other is phenyl or mono- or di-sulfophenyl,the phenyl and sulfophenyl being unsubstituted or substituted by alkylhaving 1 to 4 carbon atoms, carboxy or halogeno, with the proviso thatZ₁ is located at m- or p-position to the azo group when D is phenylene.2. The compound according to claim 1, wherein X is amino represented bythe formula (II).
 3. The compound according to claim 2, wherein any oneof R₁ and R₂ in the formula (II) is methyl or ethyl, and the other isphenyl unsubstituted or substituted by alkyl having 1 to 4 carbon atoms,alkoxy having 1 to 4 carbon atoms, sulfo, carboxy or halogeno.
 4. Thecompound according to claim 2, wherein any one of R₁ and R₂ in theformula (II) is hydrogen, and the other is phenyl or mono-ordi-sulfophenyl, the phenyl and sulfophenyl being unsubstituted orsubstituted by alkyl having 1 to 4 carbon atoms, carboxy or halogeno. 5.The compound according to claim 1, wherein X is pyridinio which isunsubstituted or substituted by carboxy or carbamoyl.
 6. The compoundaccording to claim 1, wherein D is ##STR24## in which the linkageasterisked bonds to the azo group.
 7. The compound according to claim 1,which is represented by the following formula (IV) in the free acidform, ##STR25## wherein R, Z₁ and Z₂ are as defined in claim 1, R₃ ishydrogen, methyl or ethyl, and R₄ is hydrogen, methyl, ethyl, sulfo orchloro.
 8. The compound according to claim 1, which is represented bythe following formula (V) in the free acid form, ##STR26## wherein R, Z₁and Z₂ are as defined in claim 1, R₅ is hydrogen, methyl or ethyl, andR₆ is hydrogen, methyl, ethyl, sulfo or chloro.
 9. The compoundaccording to claim 1, which is represented by the following formula (VI)in the free acid form, ##STR27## wherein R, Z₁ and Z₂ are as defined inclaim 1, and R₇ is hydrogen, carboxy or carbamoyl.
 10. The compoundaccording to claim 1, wherein Z₁ and Z₂ independently of one another areeach vinylsulfonyl or β-sulfatoethylsulfonyl.
 11. The compound accordingto claim 1, wherein R is hydrogen, methyl or ethyl.
 12. The compoundaccording to claim 8, which is represented by the following formula inthe free acid form, ##STR28##
 13. The compound according to claim 8,which is represented by the following formula in the free acid form,##STR29##
 14. The compound according to claim 4, which is represented bythe following formula in the free acid form, ##STR30##